Sequential Post-Synthetic Modification and Evaluation of Catalytic Activity of Hierarchically Porous Sulfated Geopolymer in the Oxidative Desulfurization of Dibenzothiophene

A novel sulfated hierarchically porous geopolymer catalyst for the oxidation of dibenzothiophene was prepared through sequential treatment with desilication, ion-exchange and sulfation techniques. Desilication and ion-exchange treatments were aimed at the creation of hierarchical porosity and controlling the surface area of the geopolymer, while sulfation treatment was primarily done to enhance the acidity of the hierarchically porous geopolymer. The properties of the catalyst obtained after the modifications was studied by BET, NH3-TPD, SEM, TEM, XRD, FTIR and XRF analyses. As a result of the proposed sequential treatment, the activity of the geopolymer towards the oxidation of dibenzothiophene was profoundly increased and reflected in the enhanced conversion from 14 to 85%. A plausible electronic mechanism proposed for the reaction accentuated that the reaction might take place in two stages: the formation of sulfated geopolymer peroxo complex as the active catalyst and nucleophilic attack by dibenzothiophene over the peroxo complex to form the product, both were elaborated with suitable kinetic model. The interaction between dibenzothiophene and peroxo complex was considered to be of primary concern, based on which, Langmuir-Hinshelwood kinetic model was developed. Effective regeneration upto three cycles emphasized its potential to be exploited as an efficient catalyst for oxidative desulfurization.

Automated summary

A novel sulfated hierarchically porous geopolymer catalyst was prepared through sequential desilication, ion-exchange and sulfation techniques, resulting in significantly increased oxidation activity towards dibenzothiophene. The proposed electronic mechanism suggested a two-stage reaction process, with the catalyst formation and nucleophilic attack both elucidated with suitable kinetic models. Effective regeneration after three cycles demonstrated the potential for efficient oxidative desulfurization.